Method of processing animal hair,fur and woolen textile

ABSTRACT

A process for setting animal hair material by first treating the material with an alkaline solution and then with an aqueous solution of a water-soluble compound of a metal forming a colorless complex with the animal hair, such as calcium, aluminum, lanthanum and zirconium.

United States Patent [191 Umezawa et al.

[ Oct. 8, 1974 METHOD OF PROCESSING ANIMAL HAIR,

' I FUR AND WOOLEN TEXTILE [75] Inventors: Fumio Umezawa, Tokyo; Yuji I-Iazaka, Fujisawa, both of Japan [73] Assignees: Fumikiko Umezawa; Hidefumi -Umezawa, both of Tokyo, Japan [22] Filed: Jan. 18, 1972 [21] Appl.'No.: 218,679

Related US. Application Data [63] Continuation-impart of Ser. No. 704,520, Feb. 12,

1968, abandoned.

[52] US. Cl. 8/l27.5l, 8/128 [51] Int. Cl A61k 7/10 [58] Field of Search 8/127.51-, 128, 94.14, 127.5; 252/D1G. I1, DIG. 12

[56] References Cited UNITED STATES PATENTS 2,382,632 8/1945 Hessel ct al.... 8/128 X 2,890,926 6/1959 Pardo et al. 8/128 3,019,171 1/1962 Block etal 195/68 3,059,990 10/1962 Koenig et a1 8/128 3,079,213 2/1963 Mendelsohn et al. 8/128 X' 3,193,463 7/1965 Schweizer 8/l27.51 X 3,266,994 8/1966 1 Rciss et a1 8/127.5l 3,472,783 10/1968 Smillie et a1. 252/89 FOREIGN PATENTS OR APPLICATIONS 5/1927 Great Britain 252/DIG. 12

(JJllLBP/uttufi) K113121131 5 55 2'0 Elongat on (PCI'CCTlt) 1,033,229 6/1966 Great Britain 252/DIG.12

OTHER PUBLICATIONS Cadwell et al., The Mechanism of Setting of Wool in Alkaline Solutions, Textile Research Journal, Nov. 1964, pp. 933-939.

' Roberts et al., Basic Principles of Organic Chemis- Primary Examiner-Thomas J. Herbert, Jr. Attorney, Agent, or FirmWilliam J. Daniel [5 7 ABSTRACT A process for setting animal hair material by first treating the material with an alkaline solution and then with an aqueous solution of a water-soluble compound of a metal forming a colorless complex with the animal hair, such as calcium, aluminum, lanthanum and zirconium.

5 Claims, 1 Drawing Figure PATENTEDum 8 $74 (JQHLQP/HLWE) K119121121 a 2 Elongation (Ftrcc'nt) METHOD OF PROCESSING ANIMAL HAIR, FUR

AND WOOLEN TEXTILE This application is a continuation-in-partof applicasetting process using steam or hot water, or chemical setting process using thioglycolate and bromide in combination, of persulfate, has been already known. These known processes are conducted for the purpose of preventing crimple of animal hair which is inherent to the animal hair, or which would be given during the any given stages of processing of the hair for the final product from raw material. Said known processes are also conducted for the purpose of setting pleats on the woolen textile.

As far as the fur is concerned, said known setting processes using steam, hot water, thioglycolate and bromide, etc.,' are not able to employed, for those processes might cause undesirable results of changing texture of fur, removing hair from fur, and degrading skin of fur. Accordingly, for setting fur, it is employed such 'process as coating the fur with protective material such as glycerin, arranging the lie of hair and then pressing the fur.

The hair of fur, especially coase hair has a tendency of easy to crimple in natural condition, and it is apt to crimple especially in a course of dyeing. As the results of said tendency, quality of the fur may be remarkably degraded due to angle like shape crimple formed at the tip of hair, or irregular wave like pattern formed on the whole surface of the fur. Said tendency of the fur is especially noticeable in the case of fur of fox.

As said above, the known setting process is able to carried relatively easy, but is accompanied by undesirable effect of degrading the animal hair goods.

Another process also has been known for shrinkproofing and feltproofing of sheep wool. The said process comprises treating the sheep wool with alkaline solution and then treating it with chromium complex salt of carboxylic acid. However, the process provides the intended effect but the process is not satisfactorily employed as thecommercial process, for it causes coloring of the treated sheep wool due to the color of chromium ion.

Accordingly, an object of this invention is to provide an effective setting process of animal hair goods including animal hair, fur and woolen textile, without injuring inherent properties of animal hair such as feeling, texture, color etc.

The other object of this invention is to provide aprocess for forming a stable chelate compound of keratin protein of animal hair and heavy metal, by arranging the configuration of thekeratin protein molecule so as to make the keratin easy to form the chelate compound with the heavy metal, and then reacting so arranged keratin protein with an aqueous solution of the water soluble heavy metal salt.

Another object of thisinvention is to provide a com position utilized for rearranging the configuration of keratin protein and forming the chelate compound of the keratin and heavy metal at the same time.

Further object of this invention will be obvious from the description hereinafter. a

It has been found that the animal hair goods may be set without injuring the inherent properties of the animal hair, by treating the animal hair goods with an aqueous solution containing at least one of alkaline substance selected from the group consisting of hydroxide, carbonate and bicarbonate of sodium, potassium and ammonium and lower alkanol amine, and

then treating further with an aqueous solution of water soluble metal compound of a metal selected from the group consisting of calcium, tin, aluminum, lanthanum, and zirconium.

Further it has been found that the animal hair goods may easily be set up in the single step treatment using an aqueous solution containing the first constituent selected from the group consisting of hydroxide, carbonv ate and bicarbonate of sodium, potassium and ammonium, and lower alkanol amine, and the second constituent selected from the group consistingof water soluble compounds of calcium, tin, aluminum, lanthanum and'zirconium, in the presence of a complex compound forming substance having less complex-forming capability than the keratin protein melecule, such as amino acid, peptide and enzyme.

. Still further, it has been found that said setting of the animal hair goods may be conducted more effectively by incorporating into said treating solution nonionic or anionic surface active agent.

The process of this invention comprises: treating animal-hair goods with an aqueous solution containing at least one of compound selected from the group consisting of hydroxide, carbonate and bicarbonate of sodium, potassium and ammonium, or at least one of lower alkanol amine, to rearrange the configuration of the keratin protein of animal hair and to make easythe formation of chelate compound with the metal compound used, in the first stage of the process; and further treating with an aqueous. solution of water soluble compound of a metal selected from the group'consisting of calcium, tin, aluminum, lanthanum and zirconium, so as to form chelate compound with the keratin having rearranged configuration and the metal, in the second stage of the process.

The treating solution used in the first stage of this process is the aqueous solution containing at least one of the alkaline substances selected from the group consisting of hydroxide, carbonate, and bicarbonate of sodium, potassium and ammonium, or at least one of lower alkanol amine such as monoethanol amine, diethanol amine, and triethanol amine, in a concentration of the range from 0.1 to 5% by weight. When the concentration of the alkaline substance in above solution is less than 0.1% by weight, insufficient rearrangement The treatment of theanimal hair goods in the first stage is conducted by contacting the animal hair goods with the treating solution at a temperature of 3060C for a period of 3" minutes. Whenthe treatment is conducted at a temperature below 30C orfor a period of less than 3 minutes,'excellent setis not achieved due to the insufficient rearrangement of configuration of the keratin protein molecule, While, where said the first stage treatment is carried at a'temperature above 60"C or for a period of more than 10 minutes, the anim l ha sixljat siavd de d d- Into said first stage treating solution, it is preferredto add nonionic or anionic surface activeagent in an amount of the range from 0.5 to 3% by weight, for said surfaceactive agent added accelerates the rearrangement of the configuration of the keratin molecule. As said nonionic or anionic surface active agent, sulfuric acid ester of higher alcohol, polyoxy alkylene ether,

polyoxy alkylene ester and the like are preferred. The

cationic surface active agent cannot be used in this [process as it forms precipitation together with metal ion used in the next stage of the treatment. Into the process to form chelate compound, is an aqueous solu-.

tion containing water soluble compound of calcium,

tin, aluminum, lanthanum orzirconium-. Illustrative water soluble compounds of said metals include: chloride, sulfate, hydroxide and organic acid saltof said metals, such as calcium chloride, tinchloride, alumi- 1 50. Into the treating solution used in the second stage of this process, nonionic or anionic surface active agent may further be added soas to accelerate the setting of the animal hair goods. Said surface active agent may be added in an amount of the range from 0.5 to 3% by Alaska..-

By the said tr atment of the second stage of the process, it is estimated that the chelate structures are formed through the bondage of the metal ions used and lone pair electron having atoms such as sulfur, nitrogen and oxygen in the keratin protein of the animal hair. When the said chelate structure is related with nitrogen atoms and the metal, the following structual formula is estimated; l

wherein 1 RR and R" stand for amino'acid residues. As said above, in the process of this invention it is necessary to use two of treatingsolution in principle, one of which is the solution containing alkaline substance for 'l the purpose of rearranging the configurationof the keratin molecule, and the other is, the solution containing metal ion for the formation of chelate compound. If the animal hair goods is treated using a single solution containing both said alkaline substance and metal ion, one

,used as the treating solution, one can conduct both the rearrangement of the configuration of the keratin molecule and the formation of the chelate compound in a single step of the treatment. As the treating solution for this single step treatment, such an aqueous solution containing at least one of alkaline substance selected from the group consisting of hydroxide, carbonate and bicarbonate of sodium, potassium and ammonium, or at least one of lower alkanol amine, in an amount of 0.1 5% by weight, a compound selected from the group consisting ofwater soluble compound of calcium, tin, aluminum, lanthanum and zirconium, in an amount of 0.1 5% by weight, and a stabilizer selected from the group consisting of amino acid, peptide and enzyme,in an amount of 0.1 l%'by weight, ispreferred. Further into the solution, above-stated nonionic or anionic surface active agent, and above-stated buffer agent may also be incorporated. The animal hair goods treating condition using the'single treating solution, is almost identical with the said two treating solution process, except a somewhat longer treating time is used.

The animal hair goods so treated in accordance with the process of this invention, are then washed in several times by warm water of 30- 50C or more, soapedv by using a nonionic or anionic surface active agent solution of 0.1 40.5% concentration, rinsed again by water completely, and then dried at a mild temperature of less than 100C. In this manner, the animal hair goods having substantially the same color, luster, and feeling as the untreated animal hair goods, but having an excellent setting effect, are obtained.

It is observed that many. of animal hair goods once set by the conventional process, are easily deformed when they are immersed in a hot water of 50C for a few minutes, while the animal hair goods being set in accordance with this process, are not deformed but kept their set form even after immersing them into a hot water of C for more than 10 minutes.

obtained by this process into the original form of them,

' one can treat them with a solution containing 0.1 2%

of .chelating agent such as sodium ethylene diamine tetraacetate, 8-oxyquinoline, nitrilo triacetic acid and the like, to decompose the chelate structure of keratin I ing examples, which are given merely by the way of illustration and not limitation. in the following example, all parts or percentage are given by weight. In the following example, set efficiency is determined in the manner detailed below;

Sample yarn of L mm length is wound on a glass rod of 3.5 mm in diameter, and the so wound yarn is settinished. Then the length of so set-finished yarn is measured. When found length is L mm, the apparent set efficiency E is obtained by the following formula:

E =L- L'/L X100 Example 1.

Two of the treating solutions having the following composition were prepared: 1

The first treating solution:

Triethanol amine Sodium lauryl sulfate Water 0.5 parts 0.3parts balanceflo give 100 parts of solution:

The second treating solution:

Calcium oxide l part Polyoxyethylene laurate 0.5 parts Disodium hydrogen phosphate 0.3 parts balance(to give I parts of solution) Water Wool yarn was wound around a glass rod, and was immersed in the first treating solution heated at about 40C for 3 minutes. Then so treated wool yarn'was immersed in the second treating solution heated at about 40C for 5 minutes, washed with water, soaping-treated in the known manner and then dried. In this manner the wool yarn being set-finished in spiral form was obtained. The yarn so obtained had the same color, texture and feeling as the untreated yarn.

Then the apparent and true set efficiency of so settinished wool yarn, and of wool yarn being set-finished in conventional manner of heating the yarn at 120C for 5 minutes in air, were determined and compared. The results obtained are shown in the following table:

Then the elongation-load curve of said samples were determined. The results are shown in FIGFI.

As apparent from said results, the wool yarn being treated in accordance with this process has bigger strength and elongation than the wool yarn being treated by the conventional process.

Example 2.

In this example, two of the treating solutions having the following composition, were prepared:

The first treating solution:

Disodium hydrogen phosphate 1.0 part Sodium hydroxide 0.l part Diethanol amine salt 0.3 parts of lauryl sulfate Water balnnceflo give I00 parts of solution) The second treating solution:

Stannic chloride Polyethylene alkyl ether Water 0.3 parts 0.2 parts balance(to give I00 parts of solution) Wool cloth was immersed in the first treating solution heated at about 40C for 3 minutes, squeezing off the solution from the cloth, and then the cloth was folded and pleated. So pleated cloth was then immersed in the second treating solution heated at about 40C for 1 minute, washed with water, and soaping treated. After drying, the set cloth having pleats was obtained. There was no change in color of the so obtained cloth compared with the untreated cloth.

The set efficiency of so treated cloth, together with of the cloth being set only by using the second treating solution, for the comparison, were determined. The results obtained are shown in the following table:

by only 2nd treating solution Example 3. I

Fur of mutton was treated with 3% aqueous solution of monoethanol amine at 40C for 3 minutes in the first place. Then the fur was brushed to stretch out the-crimples of the hair and to arrange the lie of the hair of the fur. Onto so treated fur, a paste consisting of 0.5 parts of aluminum potassium sulfate, 0.2 parts of alkylol amide, 6 parts of carboxymethyl cellulose and 93.3 parts of water, was coated. The paste coated fur was steamtreated for 2 minutes. Then the fur was soapingtreated, washed to remove the paste and dried. In this manner. crimpled hair of the fur was able to stretch'out without spoiling and injuring the fur. Example 4.

In this example, two of the following treating solu-.

tions having the following composition, were prepared:

The first treating solution:

parts of solution) The second treating solution:

. 'lhesecond treating solution:

' -Continued Zirconium acetate 0.1 part Diethanol amine 0.3 parts Polyoxyethylene alkyl ether 0.3 parts bulancet to give 100 .Water partsof solution) Wool yarn was set as the same manner described in the Example 1, by treating it with the first treating solution heated-at about 35 C for minutes, and then treating it with the second treating solution heated at about 55C for 5 minutes. Then the yarn was washed and dried'as the same manner as'the Example 1. So obtained wool yarn had the true set efficiency of 55%.-

Example 5. Wool cloth was treated as the same manner described in'the Example 2, but treating it with the first The first treating solution; 0.3 parts Monoethanol-amine Ammonium carbonate 0.5 parts Diethanol amine salt 0.3 parts of lauryl sulfate Water b'alance(to give 100) parts of solution) 0.5 parts 0.2 parts balanceflo give 100 parts of solution) Lanthanum chloride Polyoxycthylene alkyl ether Water 7 Example 6.

Into an aqueous solution containing 1.5% glycine and 0.5% zirconium acetate, sodium carbonate was added to adjust the pH of the solution to 10. Into the solution, wool cloth previously finely pleated was immersed at 45C for 10 minutes. So treated cloth was washed with hot water, soaping-treated and dried to give finely pleated cloth. The cloth had the true set efficiency at 71%.

Example 7.

Into an aqueous solution containing 2% amylase, and 0.5% aluminum potassium sulfate, monoethanol amine was added to adjust the pH of the solution to 8. Into the solution, hair of yak, being coiled on glass rod, was immersed while maintaining the solution at 40C. After 5 minutes, the hair was taken out from the solution, washed with hot water, soaping-treated, and then dried. In this manner the hair of yak was set in spiral form without injuring the hair which isknown very fragile to alkali.

We claim: v I. A process for setting textile material formed of animal hair which comprises: arranging said textile material'in a prede ermined configuration and while maintaining said configuration, first treating the animal hair goods with an aqueous solution consisting essentially of at least one of alkaline substances selected from the group consisting of hydroxide, carbonate and bicarbonate of sodium, potassium and ammonium, and lower alkanol amines ina concentration of the range 'from 0.1 to 5% by weight, said solution being adjusted to a pH of the range from 9.0 to 10.5, in' the first'stage. treatment; and then treating the thus treated animal hair goods with an aqueous solution consisting essentially of a water soluble salt with an organic or carboxylic acid of a heavy metal selected from the group consisting of calcium, aluminum, tin, lanthanum andzirconium forming a colorless complex with said animal hair.

2. A process for setting textile materialformed of animal hair which comprises: arranging said textile material in a predetermined configuration and while maintaining said configuration, treating the animal hair goods with an aqueous solution consisting essentially of at least one of alkaline substances selected from the group consisting of hydroxide, carbonate and bicarbonate and sodium, potassium and ammonium, and lower alkanol amines in a concentration of the range from 0.1 to 5% by weight; a water soluble salt with an inorganic or carboxylic acid of a heavy metal forming a colorless complex with saidanimal hair, in a concentration of the range from 0.1 to 5% by weight; and at least one of stabilizer compounds selected from the group consisting of amino acid, peptide and enzyme in a concentration of the range from 0.1 to 1% by weight.

3. The process of claim 2 wherein said heavy metal is selected from the group consisting of calcium, aluminum, tin, lanthanum and zirconium.

4. A composition for setting textile material formed of animal hair consisting essentially of l) at least one alkaline substance selected from the group consisting of hydroxide, carbonate and bicarbonate of sodium, potassium and ammonium, and lower alkanol amines, (2) a water soluble salt with an inorganic or carboxylic acid of a heavy metal forming a colorless complex with said animal hair, and (3) at least one stabilizer compound selected from the group consisting of amino acid, peptide and enzyme.

5. The composition of claim 4 wherein said heavy metal is selected from the group consisting of calcium, aluminum, tin, lanthanum and zirconium.

UNITED STATES PATENT OFFICE I CERTIFICATE OF CORRECTION Patent No. 3 r 840 r Dated October 8 197 4 Inventor(s) Fumio UME ZAWA et al It is certified that error appears in the aboveidentified patent and that said Letters Patent are hereby corrected as shown'below:

In the Heading of the Patent, insert [30] Foreign Application Priority Data February 18, 1967. .Japan. .l0320/l967 Signed and sealed this 4th day of March l975.

(SEAL) Attest:

C. MARSHALL DANN RUTH C. MASON Commissioner of Patents Attesting Officer and Trademarks FORM POI-1050 (10-69) USCOMM'DC 50375-P69 U.S. GOVERNMENT PRINTING OFFICE: I969 O-'35G-334 

1. A PROCESS FOR SETTING TEXTILE MATERIAL FORMED OF ANIMAL HAIR WHICH COMPRISES: ARRANGING SAID TEXTILE MATERIAL IN A PREDETERMINED CONFIGURATION AND WHILE MAINTAINING SAID CONFIGURATION, FIRST TREATING THE ANIMAL HAIR GOODS WITH AN AQUEOUS SOLUTION CONSISTING ESSENTIALLY OF AT LEAST ON OF ALKALINE SUBSTANCES SELECTED FROM THE GROUP CONSISTING OF HYDROXIDE, CARBONATE AND BICARBONATE OF SODIUM, POTASSIUM AND AMMONIUM, AND LOWER ALKANOL AMINES IN A CONCENTRATION OF THE RANGE FROM 0.1 TO 5% BY WEIGHT, SAID SOLUTION BEING ADJUSTED TO A PH OF THE RANGE FROM 9.0 TO 10.5, IN THE FIRST STAGE TREATMENT; AND THEN TREATING THE THUS TREATED ANIMAL HAIR GOODS WITH A AQUEOUS SOLUTION CONSISTING ESSENTIALLY OF A WATER SOLUBLE SALT WITH AN ORGANIC OR CARBOXYLIC ACID OF A HEAVY METAL SELECTED FROM THE GROUP CONSISTING OF CALCIUM, ALUMINUM, TIN, LANTHANIUM AND ZIRCONIUM FORMING A COLORLESS COMPLEX WITH SAID ANIMAL HAIR.
 2. A process for setting textile material formed of animal hair which comprises: arranging said textile material in a predetermined configuration and while maintaining said configuration, treating the animal hair goods with an aqueous solution consisting essentially of at least one of alkaline substances selected from the group consisting of hydroxide, carbonate and bicarbonate and sodium, potassium and ammonium, and lower alkanol amines in a concentration of the range from 0.1 to 5% by weight; a water soluble salt with an inorganic or carboxylic acid of a heavy metal forming a colorless complex with said animal hair, in a concentration of the range from 0.1 to 5% by weight; and at least one of stabilizer compounds selected from the group consisting of amino acid, peptide and enzyme in a concentration of the range from 0.1 to 1% by weight.
 3. The process of claim 2 wherein said heavy metal is selected from the group consisting of calcium, aluminum, tin, lanthanum and zirconium.
 4. A composition for setting textile material formed of animal hair consisting essentially of (1) at least one alkaline substance selected from the group consisting of hydroxide, carbonate and bicarbonate of sodium, potassium and ammonium, and lower alkanol amines, (2) a water soluble salt with an inorganic or carboxylic acid of a heavy metal forming a colorless complex with said animal hair, and (3) at least one stabilizer compound selected from the group consisting of amino acid, peptide and enzyme.
 5. The composition of claim 4 wherein said heavy metal is selected from the group consisting of calcium, aluminum, tin, lanthanum and zirconium. 